CN115521195B - Preparation method of fluorene formaldehyde compound - Google Patents

Preparation method of fluorene formaldehyde compound Download PDF

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CN115521195B
CN115521195B CN202211241964.6A CN202211241964A CN115521195B CN 115521195 B CN115521195 B CN 115521195B CN 202211241964 A CN202211241964 A CN 202211241964A CN 115521195 B CN115521195 B CN 115521195B
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fluorene
formaldehyde
preparation
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CN115521195A (en
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刘雪松
朱洋
季菲
魏万国
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Shanghai Rukun New Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

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Abstract

The invention provides a preparation method of fluorene formaldehyde compounds, which comprises the following steps: and mixing the compound shown in the formula I with a metal compound and halogenated methyl ether for reaction to obtain an intermediate shown in the formula II, and then mixing and hydrolyzing the reaction solution with water to obtain the fluorene formaldehyde compound. The preparation method provided by the invention is simple, has few process steps, and has high yield and high product purity.

Description

Preparation method of fluorene formaldehyde compound
Technical Field
The invention belongs to the field of new material synthesis, and particularly relates to a preparation method of a fluorenyl formaldehyde compound, in particular to a preparation method of a fluorenyl formaldehyde compound with high yield.
Background
Fluorene and its derivatives have a specific rigid in-plane biphenyl structure (fluorene ring), and thus have wide application in the fields of photoelectric materials, biological medicines, polymer synthesis, and the like. The fluorene derivative is a conjugated system easy to polarize, and can increase the multiphoton absorption section through chemical modification, so that the fluorene derivative is applied to an organic two-photon absorption material; and polyfluorene derivatives are very important polymer luminescent materials. Scientists conduct modification research on fluorene by adjusting the light-emitting performance of the fluorenyl material to obtain light-emitting materials with different light-emitting colors, such as blue light materials, green light materials, red light materials and the like.
The preparation methods of fluorene-2-formaldehyde and analogues thereof reported in the current literature mainly comprise the following steps:
(1) Fluorene-2-formaldehyde can be prepared from fluorene-2-methylamine and urotropine through Sommelet reaction, but raw material fluorene-2-methylamine is expensive and not easy to obtain, has high cost, generates a large amount of acid wastewater, and is not suitable for mass production (Journal of the Chemical Society,1950,2141-5).
(2) The fluorene and the N-methyl-N-phenylcarbamoyl chloride react to obtain a Friedel-crafts reaction intermediate, and then aluminum lithium hydride is used for reduction to prepare fluorene-2-formaldehyde, the total yield of the two steps of reaction is only 36%, but the cost of the N-methyl-N-phenylcarbamoyl chloride is higher, and aluminum lithium hydride with higher danger is also used, so that the method is not beneficial to industrial production.
(3) From DMF and POCl 3 The Vilsmeier-Haack reagent is prepared, the dosage is 3 molar equivalents, raw material fluorene is added at 0-5 ℃, then about 10 times of silica gel is added, the mixture is uniformly stirred and mixed by a glass rod, finally, the mixture reacts under microwave radiation, and the final product fluorene-2-formaldehyde is obtained after post-treatment and recrystallization. The reaction is carried out in the absence of a solvent, has poor fluidity, is difficult to operate, generates a large amount of waste solids, and is not suitable for mass production.
In summary, as the prior preparation process of fluorene-2-formaldehyde and analogues thereof needs to use fluorene-2-methylamine or N-methyl-N-phenylcarbamoyl chloride which is a raw material with higher price, and a large amount of acid wastewater is generated by the reaction, the preparation process has high requirements on equipment, complicated operation procedures, large environmental pollution, poor reaction selectivity, more byproducts, adverse product refining and purification, poor reaction reproducibility and adverse industrial production. Therefore, how to provide a preparation method of fluorene-2-formaldehyde and analogues thereof with few reaction procedures and high yield is a problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of fluorene formaldehyde compounds, in particular to a preparation method of fluorene formaldehyde compounds with high yield. The preparation method provided by the invention is simple, has few process steps, and has high yield and high product purity.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a preparation method of a fluorene formaldehyde compound, which has the structure shown as follows:
the preparation method comprises the following steps:
and mixing the compound shown in the formula I with a metal compound and halogenated methyl ether for reaction to obtain an intermediate shown in the formula II, and then mixing and hydrolyzing the reaction solution with water to obtain the fluorene formaldehyde compound.
Wherein R is 1 、R 2 Independently selected from any one of H, C-C12 substituted or unsubstituted alkyl, C2-C12 substituted or unsubstituted alkenyl, C6-C12 aryl, halogen and C1-C12 substituted or unsubstituted alkoxy; alternatively, R 1 Or R is 2 Either one is selected from methylene and the other is absent.
R 3 Selected from H, C C1-C12 substituted or unsubstituted alkyl, C2-C12 substituted or unsubstituted alkenyl, C6-C12 arylOne of the group consisting of a halogen, a C1-C12 substituted or unsubstituted alkoxy, and a C1-C12 substituted or unsubstituted alkylamino, and X is Cl or Br.
The substituted group is selected from any one of C1-C12 alkyl, C2-C12 alkenyl, C6-C12 aryl, halogen, C1-C12 alkoxy or C1-C12 alkylamino.
Wherein C1-C12 represents a structure containing one carbon atom, two carbon atoms, three carbon atoms and the like, and the description is omitted, wherein C1-C12 unsubstituted alkyl groups can be methyl, ethyl, propyl, isopropyl, n-butyl, tertiary butyl, isobutyl and the like, C2-C12 unsubstituted alkenyl groups can be vinyl, propenyl, 1-butenyl, 2-butenyl and the like, C6-C12 aryl groups can be phenyl, naphthyl, biphenyl and the like, C1-C12 unsubstituted alkoxy groups can be methoxy, ethoxy, propoxy, isopropoxy and the like, C1-C12 unsubstituted alkylamino groups can be methylamino, ethylamino, propylamino, isopropylamino and the like, and halogen can be fluorine, chlorine, bromine, iodine and the like, for example.
The halogenated methyl ether is selected from 1, 1-dichloro methyl ether or 1, 1-dibromomethyl ether.
The fluorene formaldehyde compound is directly obtained by adopting a metal compound, halogenated methyl ether and a compound shown in the formula I to directly react and then hydrolyzing the metal compound and the halogenated methyl ether through a one-pot method, and the preparation method is simple, few in process steps, high in yield, high in product purity, free of pollutants such as acid wastewater and the like, and environment-friendly.
Preferably, the reaction is carried out in a solvent comprising any one or a combination of at least two of dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride, tetrahydrofuran, nitrobenzene, carbon disulfide or sulfolane, such as a combination of dichloromethane and carbon disulfide, a combination of dichloromethane and chloroform or a combination of tetrahydrofuran and nitrobenzene, etc., but not limited to the above-listed combinations, other non-listed combinations within the above-listed combinations are equally applicable.
Preferably, the solvent is a combination of dichloromethane and carbon disulphide.
The specific combination of solvents described above can further enhance the yield and purity of the product.
Preferably, the solvent is subjected to a drying treatment prior to use.
Preferably, the metal compound includes any one or a combination of at least two of aluminum trichloride, ferric trichloride, zinc chloride, molybdenum pentachloride or antimony trichloride, for example, a combination of ferric trichloride and molybdenum pentachloride, a combination of ferric trichloride and zinc chloride or a combination of aluminum trichloride and antimony trichloride, etc., but not limited to the above-listed combinations, other non-listed combinations within the above-listed combinations are equally applicable.
Preferably, the metal compound is a combination of ferric trichloride and molybdenum pentachloride.
The combination of the specific metal compounds described above can further improve the yield and purity of the product and can also significantly reduce the cost compared to other metal compounds.
Preferably, the molar ratio of the compound shown in the formula I to the metal compound is 1 (1-5).
Preferably, the mol ratio of the compound shown in the formula I to the halogenated methyl ether is 1 (1-5).
Preferably, the temperature of the reaction is between-20 and 100 ℃ and the time is between 1 and 12 hours.
Preferably, the temperature of the hydrolysis by mixing the reaction solution with water is 0-50 ℃.
Preferably, the mixed hydrolysis is followed by a purification step comprising recrystallization or silica gel column chromatography.
The molar ratio of the compound represented by the formula I to the metal compound may be 1:1, 1:2, 1:3, 1:4, 1:5, etc., the molar ratio of the compound represented by the formula I to the halogenated methyl ether may be 1:1, 1:2, 1:3, 1:4, 1:5, etc., the reaction temperature may be-20 ℃, -10 ℃,0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, etc., the time may be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, etc., the temperature of mixing the reaction solution with water to hydrolyze may be 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃ or the like, but the reaction temperature is not limited to the above-listed values, and other non-listed values within the above numerical ranges are applicable as well.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of fluorene formaldehyde compounds, which is characterized in that a metal compound, halogenated methyl ether and a compound shown in a formula I are adopted to directly react, and then are hydrolyzed, so that the fluorene formaldehyde compounds are directly obtained by a one-pot method; meanwhile, the yield and purity of the product can be further improved and the cost is reduced by selecting a specific reaction solvent and a metal compound.
Detailed Description
In order to further describe the technical means adopted by the present invention and the effects thereof, the following describes the technical scheme of the present invention in combination with the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
All solvents in the examples below were dried before use, the yield was calculated as actual/theoretical x 100% and the purity was determined by gas chromatography, chromatographic column SK-5, column temperature 50℃and retention time 2min, heating to 150℃at a heating rate of 10℃per min, heating to 300℃at a heating rate of 20℃per min and final retention time of 10min.
Example 1
The embodiment provides a preparation method of fluorene-2-formaldehyde, which comprises the following specific steps:
into a 500mL reaction flask were added 10.0g (60.2 mmol) of fluorene, 9.8g (60.2 mmol,1.0 eq.) of anhydrous ferric trichloride, 16.4g (60.2 mmol,1.0 eq.) of anhydrous molybdenum pentachloride and 25g of dichloromethane, 25g of carbon disulfide, cooled in an ice water bath and protected with nitrogen, and 10.4g (90.3 mmol,1.5 eq.) of 1, 1-dichloromethyl ether was added dropwise to the mixture over 20min with a controlled temperature between 0 and 10 ℃. After the completion of the dripping, the temperature is raised to 50 ℃ and the mixture is stirred for 4 hours. Cooling to 0-10 ℃ in an ice-water bath, dropwise adding 40g of water into the reaction liquid, separating the liquid, extracting the water phase once with 50g of dichloromethane, merging the organic phases, drying with anhydrous sodium sulfate, filtering, concentrating to obtain a fluorene-2-formaldehyde crude product, and obtaining 10.9g of a fluorene-2-formaldehyde pure product by column chromatography, wherein the yield is 93%, and the purity is 99.8%.
Characterization data are as follows:
1 H NMR(400MHz,CDCl 3 )：δ10.05(s,1H),8.04(s,1H),7.90(s,2H),7.86(d,J＝8.0Hz,1H),7.59(d,J＝8.0Hz,1H),7.45-7.37(m,2H),3.96(s,2H).EIMS:m/z(rel intensity)194(33),165(100),139(10),115(5),82(25)。HRMS(m/z):[M] + calcd.for C 14 H 10 O,194.0732；found,194.0731。
example 2
The embodiment provides a preparation method of fluorene-2-formaldehyde, which comprises the following specific steps:
into a 500mL reaction flask was added 10.0g (60.2 mmol) of fluorene, 32.9g (120.4 mmol,2.0 eq.) of anhydrous molybdenum pentachloride and 25g of methylene chloride, 25g of carbon disulfide, cooled in an ice water bath and protected by nitrogen, and 10.4g (90.3 mmol,1.5 eq.) of 1, 1-dichloromethyl ether was added dropwise to the mixture over 20min at a temperature between 0 and 10 ℃. After the completion of the dripping, the temperature is raised to 50 ℃ and the mixture is stirred for 4 hours. Cooling to 0-10 ℃ in an ice-water bath, dropwise adding 40g of water into the reaction liquid, separating the liquid, extracting the water phase once with 50g of dichloromethane, merging the organic phases, drying with anhydrous sodium sulfate, filtering, concentrating to obtain a fluorene-2-formaldehyde crude product, and obtaining 9.8g of a fluorene-2-formaldehyde pure product by column chromatography, wherein the yield is 84%, and the purity is 99.2%.
Example 3
The embodiment provides a preparation method of fluorene-2-formaldehyde, which comprises the following specific steps:
into a 500mL reaction flask was added 10.0g (60.2 mmol) of fluorene, 19.5g (120.4 mmol,2.0 eq.) of anhydrous ferric trichloride and 25g of methylene chloride, 25g of carbon disulfide, cooled in an ice water bath and protected by nitrogen, and 10.4g (90.3 mmol,1.5 eq.) of 1, 1-dichloromethyl ether was added dropwise to the mixture over 20min at a temperature controlled between 0 and 10 ℃. After the completion of the dripping, the temperature is raised to 50 ℃ and the mixture is stirred for 4 hours. Cooling to 0-10 ℃ in an ice-water bath, dropwise adding 40g of water into the reaction liquid, separating the liquid, extracting the water phase once with 50g of dichloromethane, merging the organic phases, drying with anhydrous sodium sulfate, filtering, concentrating to obtain a fluorene-2-formaldehyde crude product, and obtaining 10.3g of a fluorene-2-formaldehyde pure product by column chromatography, wherein the yield is 88%, and the purity is 99.1%.
Example 4
The embodiment provides a preparation method of fluorene-2-formaldehyde, which comprises the following specific steps:
into a 500mL reaction flask was added 10.0g (60.2 mmol) of fluorene, 16.0g (120.4 mmol,2.0 eq.) of anhydrous aluminum trichloride and 25g of methylene chloride, 25g of carbon disulfide, cooled in an ice water bath and protected by nitrogen, and 10.4g (90.3 mmol,1.5 eq.) of 1, 1-dichloromethyl ether was added dropwise to the mixture over 20min at a temperature of between 0 and 10 ℃. After the completion of the dripping, the temperature is raised to 50 ℃ and the mixture is stirred for 4 hours. Cooling to 0-10 ℃ in an ice-water bath, dropwise adding 40g of water into the reaction liquid, separating the liquid, extracting the water phase once with 50g of dichloromethane, merging the organic phases, drying with anhydrous sodium sulfate, filtering, concentrating to obtain a fluorene-2-formaldehyde crude product, and obtaining 10.2g of a fluorene-2-formaldehyde pure product by column chromatography, wherein the yield is 87%, and the purity is 99.3%.
Example 5
This example provides a process for the preparation of fluorene-2-carbaldehyde, which is identical to example 1 except that methylene chloride is replaced with carbon disulphide of equal mass.
9.9g of fluorene-2-formaldehyde pure product is finally obtained, the yield is 85%, and the purity is 99.2%.
Example 6
This example provides a process for the preparation of fluorene-2-carbaldehyde, which is identical to example 1 except that carbon disulphide is replaced with equal mass of dichloromethane.
Finally, 10.2g of fluorene-2-formaldehyde pure product is obtained, the yield is 87 percent, and the purity is 99.3 percent.
Example 7
This example provides a process for the preparation of fluorene-2-carbaldehyde, which is identical to example 1 except that dichloromethane and carbon disulphide are replaced with tetrahydrofuran of equal mass.
9.4g of fluorene-2-formaldehyde pure product is finally obtained, the yield is 80 percent, and the purity is 99.2 percent.
Example 8
The embodiment provides a preparation method of 7-bromofluorene-2-formaldehyde, which comprises the following specific steps:
into a 500mL reaction flask was added 10.0g (40.8 mmol) of 2-bromofluorene, 13.2g (81.6 mmol,2.0 eq.) of ferric trichloride and 50g of methylene chloride, cooled in an ice-water bath and protected with nitrogen, and 7.0g (61.2 mmol,1.5 eq.) of 1, 1-dibromomethyl ether was added dropwise to the mixture over 20min at a temperature controlled between 0 and 10 ℃. After the completion of the dripping, the temperature is raised to 50 ℃ and the mixture is stirred for 4 hours. Cooling to 0-10 ℃ in an ice-water bath, dropwise adding 40g of water into the reaction liquid, separating the liquid, extracting the water phase once with 50g of dichloromethane, merging organic phases, drying with anhydrous sodium sulfate, filtering, concentrating to obtain a crude product of 7-bromofluorene-2-formaldehyde, and obtaining 8.4g of a pure product of 7-bromofluorene-2-formaldehyde through column chromatography, wherein the yield is 75%, and the purity is 99.5%.
Characterization data are as follows:
1 H NMR(400MHz,CDCl 3 )：δ10.06(s,1H),8.05(s,1H),7.92(d,J＝8.0Hz,1H),7.88(d,J＝8.0Hz,1H),7.74(s,1H),7.72(d,J＝8.0Hz,1H),7.56(d,J＝8.0Hz,1H),3.97(s,2H)。ESI-MS(m/z):295(M+Na) + ；HRMS(m/z):[M+Na] + calcd.for C 14 H 9 BrNaO,294.9734；found,294.9731。
example 9
This example provides a process for the preparation of fluorene-2-carbaldehyde, which is identical to example 1 except that the reaction temperature is 100 ℃.
Finally, 10.1g of fluorene-2-formaldehyde pure product is obtained, the yield is 86 percent, and the purity is 99.2 percent.
Example 10
This example provides a process for the preparation of fluorene-2-carbaldehyde, which is identical to example 1 except that the reaction temperature is-20 ℃.
8.4g of fluorene-2-formaldehyde pure product is finally obtained, the yield is 72 percent, and the purity is 99.0 percent.
Example 11
This example provides a method for preparing fluorene-2-carbaldehyde, which is identical to example 1 except that ferric trichloride and molybdenum pentachloride are replaced with antimony trichloride in the same amount.
Finally, 2.6g of fluorene-2-formaldehyde pure product is obtained, the yield is 22 percent, and the purity is 99.1 percent.
Example 12
This example provides a process for the preparation of fluorene-2-carbaldehyde, which is identical to example 1 except that iron trichloride and molybdenum pentachloride are replaced with equal amounts of titanium tetrachloride.
6.4g of fluorene-2-formaldehyde pure product is finally obtained, the yield is 55 percent, and the purity is 99.1 percent. 2.9g of fluorene-1-carbaldehyde as an impurity was obtained, and the yield was 25%.
Fluorene-1-formaldehyde characterization data are as follows:
1 H NMR(400MHz,CDCl3)：δ10.65(s,1H),8.58(d,J＝8.0Hz,1H),7.90(d,J＝8.0Hz,1H)，7.76(d,J＝8.0Hz,1H)，7.60(d,J＝8.0Hz,1H)，7.48-7.38(m,3H)，3.97(s,2H)。ESI-MS(m/z):217(M+Na) + ；HRMS(m/z):[M+Na] + calcd.forC 14 H 10 NaO,217.0629；found,217.0627。
example 13
This example provides a method for preparing fluorene-2-carbaldehyde, which is the same as example 1 except that iron trichloride and molybdenum pentachloride are replaced with zirconium tetrachloride in the same amount.
7.6g of fluorene-2-formaldehyde pure product is finally obtained, the yield is 65 percent, and the purity is 99.0 percent. 2.7g of fluorene-1-carbaldehyde as an impurity was obtained, and the yield was 23%.
Example 14
The embodiment provides a preparation method of 9,9' -diethyl fluorene-2-formaldehyde, which comprises the following specific steps:
into a 500mL reaction flask were charged 13.4g (60.2 mmol) of 9,9' -diethylfluorene, 9.8g (60.2 mmol,1.0 eq.) of anhydrous ferric trichloride, 16.4g (60.2 mmol,1.0 eq.) of anhydrous molybdenum pentachloride and 25g of methylene chloride, 25g of carbon disulfide, cooled in an ice water bath and protected with nitrogen, and 10.4g (90.3 mmol,1.5 eq.) of 1, 1-dichloromethyl ether was added dropwise to the mixture over 20min at a temperature of between 0 and 10 ℃. After the completion of the dripping, the temperature is raised to 50 ℃ and the mixture is stirred for 4 hours. Cooling to 0-10 ℃ in an ice-water bath, dropwise adding 40g of water into the reaction liquid, separating the liquid, extracting the water phase once with 50g of dichloromethane, merging the organic phases, drying with anhydrous sodium sulfate, filtering, concentrating to obtain a crude 9,9 '-diethyl fluorene-2-formaldehyde product, and obtaining 13.7g of a pure 9,9' -diethyl fluorene-2-formaldehyde product by column chromatography, wherein the yield is 91% and the purity is 99.4%. Characterization data are as follows: ESI-MS (M/z): 273 (M+Na) + ；HRMS(m/z):[M+Na] + calcd.for C 18 H 18 NaO,273.1255；found,273.1254。
Example 15
The embodiment provides a preparation method of 9-fluorofluorene-2-formaldehyde, which comprises the following specific steps:
into a 500mL reaction flask were charged 11.1g (60.2 mmol) of 9-fluorofluorene, 9.8g (60.2 mmol,1.0 eq.) of anhydrous ferric trichloride, 16.4g (60.2 mmol,1.0 eq.) of anhydrous molybdenum pentachloride and 25g of methylene chloride, 25g of carbon disulfide, cooled in an ice water bath and protected with nitrogen, and 10.4g (90.3 mmol,1.5 eq.) of 1, 1-dichloromethyl ether was added dropwise to the mixture over 20min at a temperature controlled between 0 and 10 ℃. After the completion of the dripping, the temperature is raised to 50 ℃ and the mixture is stirred for 4 hours. Cooling to 0-10 ℃ in an ice-water bath, dropwise adding 40g of water into the reaction liquid, separating the liquid, extracting the water phase once with 50g of dichloromethane, merging organic phases, drying with anhydrous sodium sulfate, filtering, concentrating to obtain a crude 9-fluorofluorene-2-formaldehyde product, and obtaining 11.4g of a pure 9-fluorofluorene-2-formaldehyde product through column chromatography, wherein the yield is 89%, and the purity is 99.0%. Characterization data are as follows: ESI-MS (M/z): 235 (M+Na) + ；HRMS(m/z):[M+Na] + calcd.for C 14 H 9 FNaO,235.0535；found,235.0530。
Example 16
The embodiment provides a preparation method of 9-allylfluorene-2-formaldehyde, which comprises the following specific steps:
to a 500mL reaction flask was added 12.4g (60.2 mmol) of 9-allylfluorene, 9.8g (60.2 mmol,1.0 eq.) of anhydrous ferric trichloride, 16.4g (60.2 mmol,1.0 eq.) of anhydrous molybdenum pentachloride and 25g of methylene chloride, 25g of carbon disulfide, cooled in an ice water bath and protected with nitrogen, and 10.4g (90.3 mmol,1.5 eq.) of 1, 1-dichloromethyl ether was added dropwise to the mixture over 20min at a temperature of between 0 and 10 ℃. After the completion of the dripping, the temperature is raised to 50 ℃ and the mixture is stirred for 4 hours. Cooling to 0-10 ℃ in an ice-water bath, dropwise adding 40g of water into the reaction liquid, separating the liquid, extracting the water phase once with 50g of dichloromethane, merging the organic phases, drying with anhydrous sodium sulfate, filtering, concentrating to obtain a crude product of 9-allylfluorene-2-formaldehyde, and obtaining 12.0g of a pure product of 9-allylfluorene-2-formaldehyde through column chromatography, wherein the yield is 85%, and the purity is 99.2%. Characterization data are as follows: ESI-MS (M/z): 257 (M+Na) + ；HRMS(m/z):[M+Na] + calcd.for C 17 H 14 NaO,257.0942；found,257.0938。
Example 17
The embodiment provides a preparation method of 6-chlorofluorene-2-formaldehyde, which comprises the following specific steps:
to a 500mL reaction flask was added 12.1g (60.2 mmol) of 3-chlorofluorene, 9.8g (60.2 mmol,1.0 eq.) of anhydrous ferric trichloride, 16.4g (60.2 mmol,1.0 eq.) of anhydrous molybdenum pentachloride and 25g of methylene chloride, 25g of carbon disulfide, cooled in an ice water bath and protected with nitrogen, and 10.4g (90.3 mmol,1.5 eq.) of 1, 1-dichloromethyl ether was added dropwise to the mixture over 20min at a temperature of between 0 and 10 ℃. After the completion of the dripping, the temperature is raised to 50 ℃ and the mixture is stirred for 4 hours. Cooling to 0-10 ℃ in an ice-water bath, dropwise adding 40g of water into the reaction liquid, separating the liquid, extracting the water phase once with 50g of dichloromethane, merging organic phases, drying with anhydrous sodium sulfate, filtering, concentrating to obtain a crude product of 6-chlorofluorene-2-formaldehyde, and obtaining 12.4g of a pure product of 6-chlorofluorene-2-formaldehyde by column chromatography, wherein the yield is 90 percent and the purity is 99.3 percent. Characterization data are as follows: ESI-MS (M/z): 251 (M+Na) + ；HRMS(m/z):[M+Na] + calcd.for C 14 H 9 ClNaO,251.0240；found,251.0238。
Example 18
The embodiment provides a preparation method of 7-methoxyfluorene-2-formaldehyde, which comprises the following specific steps:
into a 500mL reaction flask were charged 11.8g (60.2 mmol) of 2-methoxyfluorene, 9.8g (60.2 mmol,1.0 eq.) of anhydrous ferric trichloride, 16.4g (60.2 mmol,1.0 eq.) of anhydrous molybdenum pentachloride and 25g of methylene chloride, 25g of carbon disulfide, cooled in an ice water bath and protected with nitrogen, and 10.4g (90.3 mmol,1.5 eq.) of 1, 1-dichloromethyl ether was added dropwise to the mixture over 20min at a temperature of between 0 and 10 ℃. After the completion of the dripping, the temperature is raised to 50 ℃ and the mixture is stirred for 4 hours. Cooling to 0-10 ℃ in an ice-water bath, dropwise adding 40g of water into the reaction liquid, separating the liquid, extracting the water phase once with 50g of dichloromethane, merging the organic phases, drying with anhydrous sodium sulfate, filtering, concentrating to obtain a crude product of 7-methoxyfluorene-2-formaldehyde, and obtaining 12.3g of a pure product of 7-methoxyfluorene-2-formaldehyde through column chromatography, wherein the yield is 91%, and the purity is 99.3%. Characterization data are as follows: ESI-MS (M/z): 247 (M+Na) + ；HRMS(m/z):[M+Na] + calcd.for C 15 H 12 NaO 2 ,247.0735；found,247.0735。
Example 19
The embodiment provides a preparation method of 7-sec-butylfluorene-2-formaldehyde, which comprises the following specific steps:
into a 500mL reaction flask were charged 13.4g (60.2 mmol) of 2-sec-butylfluorene, 9.8g (60.2 mmol,1.0 eq.) of anhydrous ferric trichloride, 16.4g (60.2 mmol,1.0 eq.) of anhydrous molybdenum pentachloride and 25g of methylene chloride, 25g of carbon disulfide, cooled in an ice water bath and protected with nitrogen, and 10.4g (90.3 mmol,1.5 eq.) of 1, 1-dichloromethyl ether was added dropwise to the mixture over 20min at a temperature of between 0 and 10 ℃. After the completion of the dripping, the temperature is raised to 50 ℃ and the mixture is stirred for 4 hours. Cooling to 0-10 ℃ in an ice-water bath, dropwise adding 40g of water into the reaction liquid, separating the liquid, extracting the water phase once by using 50g of dichloromethane, combining the organic phases, drying by using anhydrous sodium sulfate, filtering, concentrating to obtain a crude product of 7-sec-butylfluorene-2-formaldehyde, and obtaining 13.1g of a pure product of 7-sec-butylfluorene-2-formaldehyde by column chromatography, wherein the yield is 87%, and the purity is 99.3%. Characterization data are as follows: ESI-MS (M/z): 273 (M+Na) + ；HRMS(m/z):[M+Na] + calcd.for C 18 H 18 NaO,273.1255；found,273.1250。
Example 20
The embodiment provides a preparation method of 7-N-methylfluorene-2-formaldehyde, which comprises the following specific steps:
into a 500mL reaction flask were charged 11.8g (60.2 mmol) of N-methylfluoren-2-amine, 9.8g (60.2 mmol,1.0 eq.) of anhydrous ferric trichloride, 16.4g (60.2 mmol,1.0 eq.) of anhydrous molybdenum pentachloride and 25g of methylene chloride, 25g of carbon disulfide, cooled in an ice water bath and protected with nitrogen, and 10.4g (90.3 mmol,1.5 eq.) of 1, 1-dichloromethyl ether was added dropwise to the mixture over 20min at a temperature of between 0℃and 10 ℃. After the completion of the dripping, the temperature is raised to 50 ℃ and the mixture is stirred for 4 hours. Cooling to 0-10 ℃ in an ice-water bath, dropwise adding 40g of water into the reaction liquid, separating the liquid, extracting the water phase once with 50g of dichloromethane, merging the organic phases, drying with anhydrous sodium sulfate, filtering, concentrating to obtain a crude product of 7-N-methylfluorene-2-formaldehyde, and obtaining 11.0g of a pure product of 7-N-methylfluorene-2-formaldehyde by column chromatography, wherein the yield is 82%, and the purity is 99.1%. Characterization data are as follows: ESI-MS (M/z): 246 (M+Na) + ；HRMS(m/z):[M+Na] + calcd.for C 15 H 13 NNaO,246.0895；found,246.0893。
Example 21
The embodiment provides a preparation method of 7- (propylene-1-yl) -9H-fluorene-2-formaldehyde, which comprises the following specific steps:
to a 500mL reaction flask was added 12.4g (60.2 mmol) of 2- (propen-1-yl) -9H-fluorene, 9.8g (60.2 mmol,1.0 eq.) of anhydrous ferric trichloride, 16.4g (60.2 mmol,1.0 eq.) of anhydrous molybdenum pentachloride and 25g of dichloromethane, 25g of carbon disulfide, cooled in an ice water bath and protected with nitrogen, and 10.4g (90.3 mmol,1.5 eq.) of 1, 1-dichloromethyl ether was added dropwise to the mixture over 20min at a temperature between 0 and 10 ℃. After the completion of the dripping, the temperature is raised to 50 ℃ and the mixture is stirred for 4 hours. Cooling to 0-10 ℃ in an ice-water bath, dropwise adding 40g of water into the reaction liquid, separating the liquid, extracting the water phase once by using 50g of dichloromethane, combining the organic phases, drying by using anhydrous sodium sulfate, filtering and concentrating to obtain a crude product of 7- (propylene-1-yl) -9H-fluorene-2-formaldehyde, and obtaining 12.1g of a pure product of 7- (propylene-1-yl) -9H-fluorene-2-formaldehyde by column chromatography, wherein the yield is 86% and the purity is 99.4%. Characterization data are as follows: ESI-MS (M/z): 257 (M+Na) + ；HRMS(m/z):[M+Na] + calcd.for C 17 H 14 NaO,257.0942；found,257.0939。
Example 22
The embodiment provides a preparation method of 9-methylene-9H-fluorene-2-formaldehyde, which comprises the following specific steps:
into a 500mL reaction flask were charged 10.7g (60.2 mmol) of 9-methylene-9H-fluorene, 9.8g (60.2 mmol,1.0 eq.) of anhydrous ferric trichloride, 16.4g (60.2 mmol,1.0 eq.) of anhydrous molybdenum pentachloride and 25g of methylene chloride, 25g of carbon disulfide, cooled in an ice water bath and protected with nitrogen, and 10.4g (90.3 mmol,1.5 eq.) of 1, 1-dichloromethyl ether was added dropwise to the mixture over 20min at a temperature controlled between 0 and 10 ℃. After the completion of the dripping, the temperature is raised to 50 ℃ and the mixture is stirred for 4 hours. Cooling to 0-10 ℃ in an ice-water bath, dropwise adding 40g of water into the reaction liquid, separating the liquid, extracting the water phase once with 50g of dichloromethane, merging the organic phases, drying with anhydrous sodium sulfate, filtering, concentrating to obtain a crude product of 9-methylene-9H-fluorene-2-formaldehyde, and obtaining 10.4g of a pure product of 9-methylene-9H-fluorene-2-formaldehyde by column chromatography, wherein the yield is 84 percent and the purity is 99.1 percent. Characterization data are as follows: ESI-MS (M/z): 229 (M+Na) + ；HRMS(m/z):[M+Na] + calcd.for C 15 H 10 NaO,229.0629；found,229.0629。
The content fully proves that the method provided by the invention can effectively realize the synthesis of fluorene formaldehyde compounds, and the product has high yield and high purity; comparing examples 1-4, 11-13, it can be seen that the present invention further improves the yield and purity of the product by employing specific metal compounds; as can be seen from comparative examples 5-7, the present invention further improves the yield and purity of the product by employing a specific combination of solvents.
The applicant states that the present invention describes the preparation method of the fluorenyl formaldehyde compound of the present invention by the above examples, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be carried out depending on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.

Claims (8)

1. The preparation method of the fluorenyl formaldehyde compound is characterized in that the structure of the fluorenyl formaldehyde compound is shown as follows:
the preparation method comprises the following steps:
mixing a compound shown in a formula I with a metal compound and halogenated methyl ether for reaction to obtain an intermediate shown in a formula II, and then mixing a reaction solution with water for hydrolysis to obtain the fluorene formaldehyde compound;
wherein R is 1 、R 2 Independently selected from any one of H, C-C12 substituted or unsubstituted alkyl, C2-C12 substituted or unsubstituted alkenyl, C6-C12 aryl, halogen and C1-C12 substituted or unsubstituted alkoxy; alternatively, R 1 Or R is 2 Any one of which is selected from methylene and the other is absent;
R 3 one selected from H, C-C12 substituted or unsubstituted alkyl, C2-C12 substituted or unsubstituted alkenyl, C6-C12 aryl, halogen, C1-C12 substituted or unsubstituted alkoxy and C1-C12 substituted or unsubstituted alkylamino, wherein X is Cl or Br;
the substituted group is selected from any one of C1-C12 alkyl, C2-C12 alkenyl, C6-C12 aryl, halogen, C1-C12 alkoxy or C1-C12 alkylamino;
the metal compound is a combination of ferric trichloride and molybdenum pentachloride;
the halogenated methyl ether is selected from 1, 1-dichloro methyl ether or 1, 1-dibromomethyl ether.
2. The method of claim 1, wherein the reaction is performed in a solvent comprising any one or a combination of at least two of dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride, tetrahydrofuran, nitrobenzene, carbon disulfide, or sulfolane.
3. The method of claim 2, wherein the solvent is a combination of methylene chloride and carbon disulfide.
4. The method of claim 2, wherein the solvent is dried prior to use.
5. The process according to claim 1, wherein the molar ratio of the compound of formula I to the metal compound is 1 (1-5).
6. The preparation method according to claim 1, wherein the molar ratio of the compound shown in the formula I to the halogenated methyl ether is 1 (1-5).
7. The method according to claim 1, wherein the reaction is carried out at a temperature of-20 to 100 ℃ for a time of 1 to 12 hours.
8. The process according to claim 1, wherein the temperature of the hydrolysis by mixing the reaction solution with water is 0 to 50 ℃.
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